CN114447128B - Method for preparing zinc yellow tin ore structure thin film solar cell absorption layer based on sulfur-free source precursor - Google Patents

Method for preparing zinc yellow tin ore structure thin film solar cell absorption layer based on sulfur-free source precursor Download PDF

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CN114447128B
CN114447128B CN202210112259.XA CN202210112259A CN114447128B CN 114447128 B CN114447128 B CN 114447128B CN 202210112259 A CN202210112259 A CN 202210112259A CN 114447128 B CN114447128 B CN 114447128B
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CN114447128A (en
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韩修训
方奕锟
刘为振
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Ganzhou Rare Gold New Material Research Institute Co ltd
Jiangxi University of Science and Technology
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Jiangxi University of Science and Technology
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    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
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Abstract

The invention provides a method for preparing a kesterite structure thin film solar cell absorption layer based on a sulfur-free source precursor, which comprises the following steps: the volume ratio of ethanolamine to DMF is 6: 4-10: 0 is used as a solvent, preparing a sulfur-free source CZT precursor solution containing Cu, zn and Sn elements, preparing the sulfur-free source CZT precursor film by a solution spin coating method, and then selenizing and/or vulcanizing the sulfur-free source CZT precursor film. The invention synthesizes a sulfur-free source CZT precursor film by adopting a novel solution method, and then the film of the absorption layer with the kesterite structure can be prepared by selenizing or vulcanizing or simultaneously selenizing and vulcanizing, and can be used for preparing a thin film solar cell. The method does not contain a sulfur source in the process of preparing the precursor, does not release sulfur-containing gas, reduces the emission of toxic gas, is simple and convenient to operate, and has good application value in the field of solar cells.

Description

Method for preparing zinc yellow tin ore structure thin film solar cell absorption layer based on sulfur-free source precursor
Technical Field
The invention relates to the field of solar cells, in particular to a method for preparing a zinc-tin-oxide-structured thin film solar cell absorption layer based on a sulfur-free source precursor.
Background
With the continuous development of human society, the demand of human beings for energy is also increasing, and the non-renewable energy is limited in quantity, and wastewater, waste gas and solid waste discharged in the use process also have great pollution to the environment. Solar energy becomes a current big research hot spot because of the advantages of green, no pollution, no region limitation and the like, and has wide prospect.
The CZTSSe semiconductor material with the kesterite structure is paid attention to because of rich earth content of constituent elements, large absorption coefficient of visible light (> 10 4cm-1), adjustable forbidden band width (1.0-1.5 eV) and high theoretical conversion efficiency (> 30%), and can be used as an absorption layer of a thin film solar cell.
Among the preparation methods of the CZTSSe thin film solar cell absorption layer, a vacuum method (an evaporation method, a sputtering method and the like) and an non-vacuum method (a spraying method, a spin coating method, a knife coating method and the like) are commonly used, and the vacuum method has higher equipment requirements, and meanwhile, the preparation cost is generally higher than that of the non-vacuum method, and the operation is more complex; the non-vacuum method is simple and convenient to operate and low in cost, and the prepared absorption layer is more uniform, so that the high-quality CZTSSe absorption layer is formed. In early preparations, most of the vacuum methods were used, and most of the vacuum methods were currently non-vacuum methods, in which spin coating with solution was widely used. However, when preparing a precursor film of a CZTSSe absorbing layer by a solution method, sulfur is introduced in many cases, and sulfur-containing gas is generated during annealing, which is relatively harmful to the environment.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a method for preparing a zinc-tin-oxide-structured thin film solar cell absorption layer based on a sulfur-free source precursor.
The invention provides a method for preparing a zinc-tin-oxide-structured thin film solar cell absorption layer based on a sulfur-free source precursor, which comprises the following steps: the volume ratio of ethanolamine to DMF is 6: 4-10: 0 is used as a solvent, preparing a sulfur-free source CZT precursor solution containing Cu, zn and Sn elements, preparing the sulfur-free source CZT precursor film by a solution spin coating method, and then selenizing and/or vulcanizing the sulfur-free source CZT precursor film.
The method successfully uses a solution spin-coating method to prepare the sulfur source-free CZT precursor film, and then the CZTSe absorbing layer film is obtained through selenization, or the CZTS absorbing layer film is obtained through vulcanization, or the CZTSe absorbing layer film is obtained through selenization and vulcanization at the same time. The synthesis method of the sulfur source-free precursor is simple and convenient to operate, high in efficiency, environment-friendly and has great development prospect, and the emission of toxic gas can be reduced. The invention discovers that ethanolamine or ethanolamine-DMF mixed solution is required to be used as the solvent through research.
Further, the volume ratio of the ethanolamine to the DMF in the mixed solution is 6:4-7:3. DMF refers to N, N-dimethylformamide.
When the volume proportion of the ethanolamine is increased, the viscosity of the precursor solution is increased, the wettability between the solution and the Mo substrate is reduced, and the film forming quality of the precursor film is reduced during spin coating; the increase in the DMF volume ratio causes the film to fall off after selenization, so that the volume ratio of ethanolamine to DMF is preferably controlled in the above range.
Further, zn/Sn=1.0-1.5 and Cu/(Zn+Sn) =0.6-0.7 in the sulfur-free source CZT precursor solution.
Further preferably, zn/sn=1.4, cu/(zn+sn) =0.65 in the sulfur-free source CZT precursor solution.
Still more preferably, the concentration of Cu element in the sulfur-free source CZT precursor solution is 0.20mol/L to 0.50mol/L, the concentration of Zn element is 0.20mol/L to 0.50mol/L, and the concentration of Sn element is 0.15mol/L to 0.30mol/L. When the concentration of the metal source in the precursor solution is different, the number of spin-coating layers is different.
Furthermore, the sulfur-free source CZT precursor solution can be used for doping alkali metal ions such as Li ions, na ions and K ions, and can also be used for doping cations such as Ag ions, ge ions and Cd ions. The performance of the absorption layer can be further improved after doping.
Further, the solution spin coating preparation process comprises: spin-coating the sulfur-free source CZT precursor solution on a molybdenum-plated soda-lime glass substrate, annealing at 300-500 ℃ for 2-10 min, and repeatedly spin-coating for 5-7 times to obtain the sulfur-free source CZT precursor film.
Further preferably, the annealing treatment temperature is 400+/-20 ℃ and the time is 4-6 min. The longer the precursor solution is annealed/dried, the more obvious the alloy phase elements of the precursor film are gathered to the surface layer, so that the element distribution in the film is uneven, and the partial component difference of the CZTSe absorption layer can be caused after selenization, thereby influencing the conversion efficiency.
Wherein the thickness of the molybdenum plating on the soda-lime glass substrate is preferably 800-1000nm.
The molybdenum-plated soda-lime glass substrate is required to be cleaned and dried before use, and the method specifically comprises the following steps: firstly, ultrasonically cleaning a molybdenum-plated soda-lime glass substrate by using a detergent aqueous solution for 15min, then ultrasonically cleaning the molybdenum-plated soda-lime glass substrate in deionized water for 15min, then ultrasonically cleaning the molybdenum-plated soda-lime glass substrate in acetone for 15min, then ultrasonically cleaning the molybdenum-plated soda-lime glass substrate in ethanol for 15min, and finally drying the molybdenum-plated soda-lime glass substrate in a drying box.
In particular embodiments of the present invention, a spin coater may be used to spin-coat a CZT precursor solution onto a cleaned molybdenum-coated soda-lime glass substrate, and then the substrate spin-coated with the sulfur-free CZT precursor solution is placed on a heated platen for annealing.
Further, the temperature rising rate of the selenization and/or the sulfuration is 0.5-5 ℃/s, the time is 10-30 min, and the temperature is 530-570 ℃. The selenization and/or the sulfidation can be carried out in a rapid heating annealing furnace, and protective gas is continuously introduced in the process.
In a preferred embodiment of the present invention, the method for preparing a kesterite structured thin film solar cell absorber layer based on a sulfur-free source precursor comprises the steps of:
(1) Mixing Cu (CH 3COO)2·H2O、Zn(CH3COO)2·2H2 O and SnCl 2·2H2 O with the solvent, and stirring until the Cu and the SnCl 2·2H2 O are completely dissolved to form a sulfur-free source CZT precursor solution;
(2) Spin-coating the sulfur-free source CZT precursor solution on a soda-lime glass substrate plated with molybdenum with the thickness of 800-1000 nm, annealing at 300-500 ℃ for 2-10 min, and repeatedly spin-coating for 5-7 times to obtain the sulfur-free source CZT precursor film;
(3) Under the condition of continuously introducing protective gas, the sulfur-free source CZT precursor film is subjected to selenization and/or vulcanization, wherein the temperature rising rate of the selenization and/or the vulcanization is 0.5-5 ℃/s, the time is 10-30 min, and the temperature is 530-570 ℃.
Among them, anhydrous stannous chloride may be used as the Sn source in the step (1), and the result of using stannous chloride hydrate is almost indistinguishable.
Further, the thickness of the absorption layer is 1-3 μm.
The invention also provides a preparation method of the thin-film solar cell, which comprises the step of preparing the absorption layer used for the thin-film solar cell by the method. The absorption layer is prepared according to the method, and then the subsequent preparation/assembly is carried out to obtain the thin film solar cell.
In a specific embodiment of the invention, the thin film solar cell has a SLG/Mo/CZT (S) Se/CdS/ZnO/ITO/Al structure, and the preparation method comprises the following steps:
(1) Adding ammonia water into the cadmium salt aqueous solution, uniformly stirring, putting the prepared absorption layer, adding thiourea aqueous solution for water bath deposition, and depositing a CdS buffer layer on the absorption layer;
(2) Depositing a layer of intrinsic zinc oxide i-ZnO on the CdS buffer layer by adopting a radio frequency magnetron sputtering method;
(3) Sputtering an ITO transparent conductive layer on the i-ZnO by adopting a radio frequency magnetron sputtering method;
(4) And preparing a grid Al electrode on the ITO transparent conductive layer by adopting a thermal evaporation method.
Preferably, the more detailed conditions are controlled as follows:
(1) Adding ammonia water into the cadmium salt aqueous solution, stirring uniformly, putting the prepared absorption layer, adding thiourea aqueous solution, performing water bath deposition at 70 ℃ for 7-10 min, depositing a CdS buffer layer on the absorption layer, washing the deposited film with a large amount of deionized water, drying, and finally drying in a drying box;
(2) Depositing a layer of intrinsic zinc oxide (i-ZnO) on the CdS buffer layer by adopting a radio frequency magnetron sputtering method, wherein the technological parameters are as follows: the sputtering gas is argon, the background vacuum is less than 5x10-4 Pa, the sputtering power is 130W, the working air pressure is 0.2Pa, and the sputtering time is 15min;
(3) Sputtering an ITO transparent conductive layer on the i-ZnO by adopting a radio frequency magnetron sputtering method, wherein the technological parameters are as follows: the sputtering gas is argon, the background vacuum is less than 5x10 -4 Pa, the sputtering power is 130W, the working air pressure is 0.12Pa, and the sputtering time is 30min;
(4) Preparing a grid Al electrode on the ITO transparent conductive layer by adopting a thermal evaporation method, wherein the technological parameters are as follows: background vacuum <5x10 -4 Pa, evaporation power supply current 120A, and evaporation time of 10min.
The invention provides a method for preparing a zinc-tin ore structure film solar cell absorbing layer based on a sulfur-free source precursor. The method does not contain a sulfur source in the process of preparing the precursor, does not release sulfur-containing gas, reduces the emission of toxic gas, is simple and convenient to operate, and has good application value in the field of solar cells.
Drawings
FIG. 1 is an XRD pattern for a CZTSe absorbing layer prepared in example 2;
FIG. 2 is a surface and cross-sectional profile of a CZT precursor film prepared in example 2, and a SEM surface and cross-sectional profile of a post-selenized CZTSe film;
FIG. 3 is a schematic view of a CZTSe thin film solar cell prepared in example 2;
FIG. 4 is a J-V plot of a CZTSe thin film solar cell prepared in example 2;
FIG. 5 is a statistical plot of the efficiency of the CZTSe thin film solar cells prepared in examples 1-5;
FIG. 6 is a graph showing statistics of the efficiency of CZTSe thin film solar cell devices prepared in example 6 using only ethanolamine as solvent;
FIG. 7 is a graph showing statistics of the efficiency of CZTSe thin film solar cell devices prepared in example 7 using a mixed solvent of ethanol and ethanol (ethanol: ethanol=7:3) as solvent;
FIG. 8 is a graph showing statistics of the efficiency of CZTSe thin film solar cell devices prepared in example 8 using DMF alone as a solvent.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The experimental reagents, materials, etc. used in the examples of the present invention are commercially available unless otherwise specified.
Unless specifically indicated, the technical means used in the embodiments of the present invention are conventional means well known to those skilled in the art.
Example 1
The embodiment provides a method for preparing a CZTSe thin film solar cell absorption layer based on a sulfur source-free precursor, which comprises the following steps:
(1) 0.93436g of Cu (CH 3COO)2·H2O、0.92194g Zn(CH3COO)2·2H2 O and 0.67695g of SnCl 2·2H2 O) were weighed and dissolved in 10mL of solvent (ethanolamine: dmf=7:3 volume ratio), completely dissolved to form a CZT precursor solution;
(2) Spin-coating a CZT precursor solution on a cleaned molybdenum-plated (800 nm) soda-lime glass substrate by using a spin coater, then placing the glass substrate on a heating table (400 ℃) for annealing for 2min, and repeatedly spin-coating for 7 times to obtain a CZT precursor film;
(3) Under the condition of continuously introducing protective gas, the obtained CZT precursor film is put into a rapid heating annealing furnace to carry out selenizing treatment, the temperature is raised to 530 ℃ for 500 seconds, and the temperature is kept for 600 seconds and then the film of the CZTSe absorption layer is naturally cooled, so that the film of the CZTSe absorption layer is obtained.
In this embodiment, the CZTSe absorbing layer film obtained above is used to continuously prepare a thin film solar cell, and the steps are as follows:
(4) Adding ammonia water into a cadmium salt aqueous solution, stirring uniformly, putting the prepared CZTSe film, adding thiourea aqueous solution, performing water bath deposition at 70 ℃ for 7-10 min, depositing a CdS buffer layer on the CZTSe film, washing the deposited film with a large amount of deionized water, drying, and finally drying in a drying box;
(5) Depositing a layer of intrinsic zinc oxide (i-ZnO) on the CdS buffer layer by adopting a radio frequency magnetron sputtering method, wherein the technological parameters are as follows: the sputtering gas is argon, the background vacuum is less than 5x10 -4 Pa, the sputtering power is 130W, the working air pressure is 0.2Pa, and the sputtering time is 15min;
(6) Sputtering an ITO transparent conductive layer on the i-ZnO by adopting a radio frequency magnetron sputtering method, wherein the technological parameters are as follows: the sputtering gas is argon, the background vacuum is less than 5x10 -4 Pa, the sputtering power is 130W, the working air pressure is 0.12Pa, and the sputtering time is 30min;
(7) Preparing a grid Al electrode on the ITO conductive layer by adopting a thermal evaporation method, wherein the technological parameters are as follows: background vacuum <5x10 -4 Pa, evaporation power supply current 120A, and evaporation time of 10min.
Example 2
The embodiment provides a method for preparing a CZTSe thin film solar cell absorption layer based on a sulfur source-free precursor, which comprises the following steps:
(1) 0.93436g of Cu (CH 3COO)2·H2O、0.92194g Zn(CH3COO)2·2H2 O and 0.67695g of SnCl 2·2H2 O) were weighed and dissolved in 10mL of solvent (ethanolamine: dmf=7:3 volume ratio), completely dissolved to form a CZT precursor solution;
(2) Spin-coating a CZT precursor solution on a cleaned molybdenum-plated soda-lime glass substrate by using a spin coater, then placing the glass substrate on a heating table (400 ℃) for annealing for 4min, and repeatedly spin-coating for 7 times to obtain a CZT precursor film;
(3) Under the condition of continuously introducing protective gas, the obtained CZT precursor film is put into a rapid heating annealing furnace to carry out selenizing treatment, the temperature is raised to 530 ℃ for 500 seconds, and the temperature is kept for 600 seconds and then the film of the CZTSe absorption layer is naturally cooled, so that the film of the CZTSe absorption layer is obtained.
In this embodiment, the CZTSe absorbing layer film obtained above is used to continuously prepare a thin film solar cell, and the steps are as follows:
(4) Adding ammonia water into a cadmium salt aqueous solution, stirring uniformly, putting the prepared CZTSe film, adding thiourea aqueous solution, performing water bath deposition at 70 ℃ for 7-10 min, depositing a CdS buffer layer on the CZTSe film, washing the deposited film with a large amount of deionized water, drying, and finally drying in a drying box;
(5) Depositing a layer of intrinsic zinc oxide (i-ZnO) on the CdS buffer layer by adopting a radio frequency magnetron sputtering method, wherein the technological parameters are as follows: the sputtering gas is argon, the background vacuum is less than 5x10 -4 Pa, the sputtering power is 130W, the working air pressure is 0.2Pa, and the sputtering time is 15min;
(6) Sputtering an ITO transparent conductive layer on the i-ZnO by adopting a radio frequency magnetron sputtering method, wherein the technological parameters are as follows: the sputtering gas is argon, the background vacuum is less than 5x10 -4 Pa, the sputtering power is 130W, the working air pressure is 0.12Pa, and the sputtering time is 30min;
(7) Preparing a grid Al electrode on the ITO conductive layer by adopting a thermal evaporation method, wherein the technological parameters are as follows: background vacuum <5x10 -4 Pa, evaporation power supply current 120A, and evaporation time of 10min.
FIG. 1 is an XRD pattern of the CZTSe absorbing layer prepared in this example; FIG. 2 is a surface and cross-sectional profile of a CZT precursor film prepared in this example, and a SEM surface and cross-sectional profile of a selenized CZTSe film; FIG. 3 is a schematic view of a CZTSe thin film solar cell prepared in this example; fig. 4 is a J-V graph of a CZTSe thin film solar cell prepared in this example.
From the above results, it can be seen that the prepared CZTSe absorbing layer contains only CZTSe, molybdenum selenide and Mo characteristic peaks, and no other secondary phase; the CZTSe absorbing layer has larger grain size and compact film, and the absorbing layer is composed of a large grain layer, a small grain layer and a carbon-rich layer from top to bottom. The presence of the carbon-rich layer results in a greater series resistance of the device, thereby affecting the performance of the device.
Example 3
The embodiment provides a method for preparing a CZTSe thin film solar cell absorption layer based on a sulfur source-free precursor, which comprises the following steps:
(1) 0.93436g of Cu (CH 3COO)2·H2O、0.92194g Zn(CH3COO)2·2H2 O and 0.67695g of SnCl 2·2H2 O) were weighed and dissolved in 10mL of solvent (ethanolamine: dmf=7:3 volume ratio), completely dissolved to form a CZT precursor solution;
(2) Spin-coating a CZT precursor solution on a cleaned molybdenum-plated soda-lime glass substrate by using a spin coater, then placing the glass substrate on a heating table (400 ℃) for annealing for 6min, and repeatedly spin-coating for 7 times to obtain a CZT precursor film;
(3) Under the condition of continuously introducing protective gas, the obtained CZT precursor film is put into a rapid heating annealing furnace to carry out selenizing treatment, the temperature is raised to 530 ℃ for 500 seconds, and the temperature is kept for 600 seconds and then the film of the CZTSe absorption layer is naturally cooled, so that the film of the CZTSe absorption layer is obtained.
In this embodiment, the CZTSe absorbing layer film obtained above is used to continuously prepare a thin film solar cell, and the steps are as follows:
(4) Adding ammonia water into a cadmium salt aqueous solution, stirring uniformly, putting the prepared CZTSe film, adding thiourea aqueous solution, performing water bath deposition at 70 ℃ for 7-10 min, depositing a CdS buffer layer on the CZTSe film, washing the deposited film with a large amount of deionized water, drying, and finally drying in a drying box;
(5) Depositing a layer of intrinsic zinc oxide (i-ZnO) on the CdS buffer layer by adopting a radio frequency magnetron sputtering method, wherein the technological parameters are as follows: the sputtering gas is argon, the background vacuum is less than 5x10 -4 Pa, the sputtering power is 130W, the working air pressure is 0.2Pa, and the sputtering time is 15min;
(6) Sputtering an ITO transparent conductive layer on the i-ZnO by adopting a radio frequency magnetron sputtering method, wherein the technological parameters are as follows: the sputtering gas is argon, the background vacuum is less than 5x10 -4 Pa, the sputtering power is 130W, the working air pressure is 0.12Pa, and the sputtering time is 30min;
(7) Preparing a grid Al electrode on the ITO conductive layer by adopting a thermal evaporation method, wherein the technological parameters are as follows: background vacuum <5x10 -4 Pa, evaporation power supply current 120A, and evaporation time of 10min.
Example 4
The embodiment provides a method for preparing a CZTSe thin film solar cell absorption layer based on a sulfur source-free precursor, which comprises the following steps:
(1) 0.93436g of Cu (CH 3COO)2·H2O、0.92194g Zn(CH3COO)2·2H2 O and 0.67695g of SnCl 2·2H2 O) were weighed and dissolved in 10mL of solvent (ethanolamine: dmf=7:3 volume ratio), completely dissolved to form a CZT precursor solution;
(2) Spin-coating a CZT precursor solution on a cleaned molybdenum-plated soda-lime glass substrate by using a spin coater, then placing the glass substrate on a heating table (400 ℃) for annealing for 8min, and repeatedly spin-coating for 7 times to obtain a CZT precursor film;
(3) Under the condition of continuously introducing protective gas, the obtained CZT precursor film is put into a rapid heating annealing furnace to carry out selenizing treatment, the temperature is raised to 530 ℃ for 500 seconds, and the temperature is kept for 600 seconds and then the film of the CZTSe absorption layer is naturally cooled, so that the film of the CZTSe absorption layer is obtained.
In this embodiment, the CZTSe absorbing layer film obtained above is used to continuously prepare a thin film solar cell, and the steps are as follows:
(4) Adding ammonia water into a cadmium salt aqueous solution, stirring uniformly, putting the prepared CZTSe film, adding thiourea aqueous solution, performing water bath deposition at 70 ℃ for 7-10 min, depositing a CdS buffer layer on the CZTSe film, washing the deposited film with a large amount of deionized water, drying, and finally drying in a drying box;
(5) Depositing a layer of intrinsic zinc oxide (i-ZnO) on the CdS buffer layer by adopting a radio frequency magnetron sputtering method, wherein the technological parameters are as follows: the sputtering gas is argon, the background vacuum is less than 5x10 -4 Pa, the sputtering power is 130W, the working air pressure is 0.2Pa, and the sputtering time is 15min;
(6) Sputtering an ITO transparent conductive layer on the i-ZnO by adopting a radio frequency magnetron sputtering method, wherein the technological parameters are as follows: the sputtering gas is argon, the background vacuum is less than 5x10 -4 Pa, the sputtering power is 130W, the working air pressure is 0.12Pa, and the sputtering time is 30min;
(7) Preparing a grid Al electrode on the ITO conductive layer by adopting a thermal evaporation method, wherein the technological parameters are as follows: background vacuum <5x10 -4 Pa, evaporation power supply current 120A, and evaporation time of 10min.
Example 5
The embodiment provides a method for preparing a CZTSe thin film solar cell absorption layer based on a sulfur source-free precursor, which comprises the following steps:
(1) 0.93436g of Cu (CH 3COO)2·H2O、0.92194g Zn(CH3COO)2·2H2 O and 0.67695g of SnCl 2·2H2 O) were weighed and dissolved in 10mL of solvent (ethanolamine: dmf=7:3 volume ratio), completely dissolved to form a CZT precursor solution;
(2) Spin-coating a CZT precursor solution on a cleaned molybdenum-plated soda-lime glass substrate by using a spin coater, then placing the glass substrate on a heating table (400 ℃) for annealing for 10min, and repeatedly spin-coating for 7 times to obtain a CZT precursor film;
(3) Under the condition of continuously introducing protective gas, the obtained CZT precursor film is put into a rapid heating annealing furnace to carry out selenizing treatment, the temperature is raised to 530 ℃ for 500 seconds, and the temperature is kept for 600 seconds and then the film of the CZTSe absorption layer is naturally cooled, so that the film of the CZTSe absorption layer is obtained.
In this embodiment, the CZTSe absorbing layer film obtained above is used to continuously prepare a thin film solar cell, and the steps are as follows:
(4) Adding ammonia water into a cadmium salt aqueous solution, stirring uniformly, putting the prepared CZTSe film, adding thiourea aqueous solution, performing water bath deposition at 70 ℃ for 7-10 min, depositing a CdS buffer layer on the CZTSe film, washing the deposited film with a large amount of deionized water, drying, and finally drying in a drying box;
(5) Depositing a layer of intrinsic zinc oxide (i-ZnO) on the CdS buffer layer by adopting a radio frequency magnetron sputtering method, wherein the technological parameters are as follows: the sputtering gas is argon, the background vacuum is less than 5x10 -4 Pa, the sputtering power is 130W, the working air pressure is 0.2Pa, and the sputtering time is 15min;
(6) Sputtering an ITO transparent conductive layer on the i-ZnO by adopting a radio frequency magnetron sputtering method, wherein the technological parameters are as follows: the sputtering gas is argon, the background vacuum is less than 5x10 -4 Pa, the sputtering power is 130W, the working air pressure is 0.12Pa, and the sputtering time is 30min;
(7) Preparing a grid Al electrode on the ITO conductive layer by adopting a thermal evaporation method, wherein the technological parameters are as follows: background vacuum <5x10 -4 Pa, evaporation power supply current 120A, and evaporation time of 10min.
Example 6
The embodiment provides a method for preparing a CZTSe thin film solar cell absorption layer based on a sulfur source-free precursor, which comprises the following steps:
(1) 0.93436g Cu (CH 3COO)2·H2O、0.92194g Zn(CH3COO)2·2H2 O and 0.67695g SnCl 2·2H2 O are weighed and dissolved in 10mL ethanolamine solvent to form a CZT precursor solution;
(2) Spin-coating a CZT precursor solution on a cleaned molybdenum-plated soda-lime glass substrate by using a spin coater, then placing the glass substrate on a heating table for annealing for 6min, and repeatedly spin-coating for 7 times to obtain a CZT precursor film;
(3) Under the condition of continuously introducing protective gas, the obtained CZT precursor film is put into a rapid heating annealing furnace to carry out selenizing treatment, the temperature is raised to 530 ℃ for 500 seconds, and the temperature is kept for 600 seconds and then the film of the CZTSe absorption layer is naturally cooled, so that the film of the CZTSe absorption layer is obtained.
In this embodiment, the CZTSe absorbing layer film obtained above is used to continuously prepare a thin film solar cell, and the steps are as follows:
(4) Adding ammonia water into a cadmium salt aqueous solution, stirring uniformly, putting the prepared CZTSe film, adding thiourea aqueous solution, performing water bath deposition at 70 ℃ for 7-10 min, depositing a CdS buffer layer on the CZTSe film, washing the deposited film with a large amount of deionized water, drying, and finally drying in a drying box;
(5) Depositing a layer of intrinsic zinc oxide (i-ZnO) on the CdS buffer layer by adopting a radio frequency magnetron sputtering method, wherein the technological parameters are as follows: the sputtering gas is argon, the background vacuum is less than 5x10 -4 Pa, the sputtering power is 130W, the working air pressure is 0.2Pa, and the sputtering time is 15min;
(6) Sputtering an ITO transparent conductive layer on the i-ZnO by adopting a radio frequency magnetron sputtering method, wherein the technological parameters are as follows: the sputtering gas is argon, the background vacuum is less than 5x10 -4 Pa, the sputtering power is 130W, the working air pressure is 0.12Pa, and the sputtering time is 30min;
(7) Preparing a grid Al electrode on the ITO conductive layer by adopting a thermal evaporation method, wherein the technological parameters are as follows: background vacuum <5x10 -4 Pa, evaporation power supply current 120A, and evaporation time of 10min.
Example 7
The embodiment provides a method for preparing a CZTSe thin film solar cell absorption layer based on a sulfur source-free precursor, which comprises the following steps:
(1) 0.93436g of Cu (CH 3COO)2·H2O、0.92194g Zn(CH3COO)2·2H2 O and 0.67695g of SnCl 2·2H2 O) were weighed and dissolved in 10mL of solvent (ethanolamine: ethanol=7:3 volume ratio), completely dissolved to form a CZT precursor solution;
(2) Spin-coating a CZT precursor solution on a cleaned molybdenum-plated soda-lime glass substrate by using a spin coater, then placing the glass substrate on a heating table for annealing for 6min, and repeatedly spin-coating for 7 times to obtain a CZT precursor film;
(3) Under the condition of continuously introducing protective gas, the obtained CZT precursor film is put into a rapid heating annealing furnace to carry out selenizing treatment, the temperature is raised to 530 ℃ for 500 seconds, and the temperature is kept for 600 seconds and then the film of the CZTSe absorption layer is naturally cooled, so that the film of the CZTSe absorption layer is obtained.
In this embodiment, the CZTSe absorbing layer film obtained above is used to continuously prepare a thin film solar cell, and the steps are as follows:
(4) Adding ammonia water into a cadmium salt aqueous solution, stirring uniformly, putting the prepared CZTSe film, adding thiourea aqueous solution, performing water bath deposition at 70 ℃ for 7-10 min, depositing a CdS buffer layer on the CZTSe film, washing the deposited film with a large amount of deionized water, drying, and finally drying in a drying box;
(5) Depositing a layer of intrinsic zinc oxide (i-ZnO) on the CdS buffer layer by adopting a radio frequency magnetron sputtering method, wherein the technological parameters are as follows: the sputtering gas is argon, the background vacuum is less than 5x10 -4 Pa, the sputtering power is 130W, the working air pressure is 0.2Pa, and the sputtering time is 15min;
(6) Sputtering an ITO transparent conductive layer on the i-ZnO by adopting a radio frequency magnetron sputtering method, wherein the technological parameters are as follows: the sputtering gas is argon, the background vacuum is less than 5x10 -4 Pa, the sputtering power is 130W, the working air pressure is 0.12Pa, and the sputtering time is 30min;
(7) Preparing a grid Al electrode on the ITO conductive layer by adopting a thermal evaporation method, wherein the technological parameters are as follows: background vacuum <5x10 -4 Pa, evaporation power supply current 120A, and evaporation time of 10min.
Example 8
The embodiment provides a method for preparing a CZTSe thin film solar cell absorption layer based on a sulfur source-free precursor, which comprises the following steps:
(1) 0.93436g Cu (CH 3COO)2·H2O、0.92194g Zn(CH3COO)2·2H2 O and 0.67695g SnCl 2·2H2 O and dissolved in 10mL DMF solvent were weighed and dissolved completely to form a CZT precursor solution;
(2) Spin-coating a CZT precursor solution on a cleaned molybdenum-plated soda-lime glass substrate by using a spin coater, then placing the glass substrate on a heating table for annealing for 6min, and repeatedly spin-coating for 7 times to obtain a CZT precursor film;
(3) Under the condition of continuously introducing protective gas, the obtained CZT precursor film is put into a rapid heating annealing furnace to carry out selenizing treatment, the temperature is raised to 530 ℃ for 500 seconds, and the temperature is kept for 600 seconds and then the film of the CZTSe absorption layer is naturally cooled, so that the film of the CZTSe absorption layer is obtained.
In this embodiment, the CZTSe absorbing layer film obtained above is used to continuously prepare a thin film solar cell, and the steps are as follows:
(4) Adding ammonia water into a cadmium salt aqueous solution, stirring uniformly, putting the prepared CZTSe film, adding thiourea aqueous solution, performing water bath deposition at 70 ℃ for 7-10 min, depositing a CdS buffer layer on the CZTSe film, washing the deposited film with a large amount of deionized water, drying, and finally drying in a drying box;
(5) Depositing a layer of intrinsic zinc oxide (i-ZnO) on the CdS buffer layer by adopting a radio frequency magnetron sputtering method, wherein the technological parameters are as follows: the sputtering gas is argon, the background vacuum is less than 5x10 -4 Pa, the sputtering power is 130W, the working air pressure is 0.2Pa, and the sputtering time is 15min;
(6) Sputtering an ITO transparent conductive layer on the i-ZnO by adopting a radio frequency magnetron sputtering method, wherein the technological parameters are as follows: the sputtering gas is argon, the background vacuum is less than 5x10 -4 Pa, the sputtering power is 130W, the working air pressure is 0.12Pa, and the sputtering time is 30min;
(7) Preparing a grid Al electrode on the ITO conductive layer by adopting a thermal evaporation method, wherein the technological parameters are as follows: background vacuum <5x10 -4 Pa, evaporation power supply current 120A, and evaporation time of 10min.
Fig. 5 is a statistical chart of the efficiency of CZTSe thin film solar cells prepared in examples 1-5, and fig. 6, 7 and 8 are statistical charts of the efficiency of CZTSe thin film solar cells prepared in examples 6, 7 and 8, respectively.
It can be seen that the CZTSe thin film solar cell prepared by using the ethanol amine-DMF mixed solution as the solvent has higher efficiency, wherein the precursor annealing treatment in the embodiment 2 is performed for 4min, the highest efficiency can reach 6.8%, but the efficiency of the device is uneven at this time, and the efficiency distribution interval is larger; when annealed for 6min in example 3, the average efficiency of the device was highest, and the efficiency profile at this time was also most uniform.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (9)

1. The method for preparing the zinc-tin ore structure thin film solar cell absorption layer based on the sulfur-free source precursor is characterized by comprising the following steps of: the volume ratio of ethanolamine to DMF is 6: and (3) taking the mixed solution of 4-7:3 as a solvent, preparing a sulfur-free source CZT precursor solution containing Cu, zn and Sn elements, preparing the sulfur-free source CZT precursor film by a solution spin coating method, and selenizing and/or vulcanizing the sulfur-free source CZT precursor film.
2. The method for preparing the zinc-tin ore structure thin film solar cell absorption layer based on the sulfur-free source precursor according to claim 1, wherein Zn/Sn=1.0-1.5 and Cu/(Zn+Sn) =0.6-0.7 in the sulfur-free source CZT precursor solution.
3. The method for preparing a kesterite structure thin film solar cell absorber layer based on a sulfur-free source precursor according to claim 2, wherein Li +、Na+、K+、Ag+, ge ions and Cd ions are doped to the sulfur-free source CZT precursor solution.
4. The method for preparing a kesterite structure thin film solar cell absorber layer based on a sulfur-free source precursor according to claim 1 or 2, wherein the solution spin-coating preparation process comprises: spin-coating the sulfur-free source CZT precursor solution on a molybdenum-plated soda-lime glass substrate, annealing at 300-500 ℃ for 2-10 min, and repeatedly spin-coating for 5-7 times to obtain the sulfur-free source CZT precursor film.
5. The method for preparing the zinc-tin ore structured thin film solar cell absorption layer based on the sulfur-free source precursor according to claim 1 or 2, wherein the temperature rise rate of selenization and/or vulcanization is 0.5-5 ℃/s, the time is 10-30 min, and the temperature is 530-570 ℃.
6. The method for preparing a kesterite structure thin film solar cell absorber layer based on a sulfur-free source precursor according to claim 1, comprising the steps of:
(1) Mixing Cu (CH 3COO)2·H2O、Zn(CH3COO)2·2H2 O and SnCl 2·2H2 O with the solvent, and stirring until the Cu and the SnCl 2·2H2 O are completely dissolved to form a sulfur-free source CZT precursor solution;
(2) Spin-coating the sulfur-free source CZT precursor solution on a soda-lime glass substrate plated with molybdenum with the thickness of 800-1000 nm, annealing at 300-500 ℃ for 2-10 min, and repeatedly spin-coating for 5-7 times to obtain the sulfur-free source CZT precursor film;
(3) And under the condition of continuously introducing protective gas, selenizing and/or vulcanizing the sulfur-free source CZT precursor film.
7. The method for preparing the kesterite structure thin film solar cell absorption layer based on the sulfur-free source precursor according to claim 6, wherein the thickness of the absorption layer is 1-3 μm.
8. A method for manufacturing a thin film solar cell, comprising the step of manufacturing an absorber layer for a thin film solar cell according to any one of claims 1 to 7.
9. The method of manufacturing a thin film solar cell according to claim 8, wherein the thin film solar cell has an SLG/Mo/kesterite structure/CdS/ZnO/ITO/Al structure, comprising the steps of:
(1) Adding ammonia water into the cadmium salt aqueous solution, uniformly stirring, putting the prepared absorption layer, adding thiourea aqueous solution for water bath deposition, and depositing a CdS buffer layer on the absorption layer;
(2) Depositing a layer of intrinsic zinc oxide i-ZnO on the CdS buffer layer by adopting a radio frequency magnetron sputtering method;
(3) Sputtering an ITO transparent conductive layer on the i-ZnO by adopting a radio frequency magnetron sputtering method;
(4) And preparing a grid Al electrode on the ITO transparent conductive layer by adopting a thermal evaporation method.
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